CN102492137B - Preparation method of photosensitive conductive polyaniline nanoparticles - Google Patents
Preparation method of photosensitive conductive polyaniline nanoparticles Download PDFInfo
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- CN102492137B CN102492137B CN201110379481.8A CN201110379481A CN102492137B CN 102492137 B CN102492137 B CN 102492137B CN 201110379481 A CN201110379481 A CN 201110379481A CN 102492137 B CN102492137 B CN 102492137B
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Abstract
The present invention provides a preparation method of photosensitive conductive polyaniline nanoparticles, which belongs to the field of functional polymer materials. The method for preparing the photosensitive polyaniline nanoparticles comprises the following steps: taking UV irradiation photo-crosslinked amphiphilic polymers micelle as polymerization template and a stabilizer, adding an initiator to polymerize an aniline monomer to obtain a solution containing the photosensitive polyaniline nanoparticles, centrifuging the solution and separating to obtain the photosensitive conductive polyaniline nanoparticles. The polyaniline enables stable dispersion in water; the obtained nano-particle dispersion has good film-forming property. The method of the present invention is simple, the yield is high, and the method is a green preparation method of photosensitive conductive polyaniline nanoparticles in an aqueous system. The size of the polyaniline particles is uniform, and the method of the invention has broad application prospect on optoelectronic devices, light-curing conductive coatings, conductive inks, sensors, nano-particle ink-jet printing, electronic shielding and stealth technology.
Description
Technical field:
The invention belongs to the preparing technical field of conducting polymer nano material, more specifically relate to a kind of preparation method of photosensitive conductive polyaniline nanoparticles.
Background technology:
Polyaniline has excellent electroactive, raw material is cheap, be easy to synthesize, simple operation and other advantages, become one of conductive polymers having most broad commercial applications prospect. but, the height aromaticity of polyaniline structure makes it have higher chemical stability and thermostability, cause solution processing or melt-processed obstacle. nanotechnology is introduced in polyaniline material, not only be expected to solve machine-shaping problem, thereby the process of industrialization of pushing guidance electric polymer, and can also make it integrate electroconductibility and nano effect, make it at sensor, light emitting diode, ultracapacitor, there is application prospect very widely in the field such as antistatic material and electromagnetic shielding material.
The preparation method of Nano particles of polyaniline mainly takes microemulsion polymerization method, dispersion copolymerization method and electrochemical polymerization method at present.In micro-emulsion polymerization, to use a large amount of emulsifying agents, cause in system polyaniline massfraction low, inefficiency, and also the method also needs to use organic solvent; Although and electrochemical process can regulate by the size and form that regulates electrochemical parameter etc. to carry out p-poly-phenyl amine nanoparticle, the quantity of Nano particles of polyaniline that electrochemical process obtains is limit by electrode area, is difficult to obtain a large amount of nanoparticles.Dispersion copolymerization method adopts polymkeric substance with a large amount of hydrophilic radicals as dispersion agent, stablizes the Nano particles of polyaniline of synthesized, avoids it in the aqueous solution, precipitate or flocculate.Conventional dispersion agent has polyvinyl alcohol, Polyvinylpyrolidone (PVP), hydroxy propyl cellulose etc.But the particle diameter and the homogeneity that adopt these polymkeric substance to be difficult to formed Nano particles of polyaniline as dispersion agent are controlled.
Parents' polymkeric substance contains hydrophilic segment and oleophylic segment simultaneously, can carry out self-assembly and form micella, by regulating the wetting ability of segment and form and the particle diameter of the ratio of lipophilicity and hydrophilic segment and oleophylic segment to micella to control in the aqueous solution.The people such as Yueh-Lin Loo obtain the blocked parents polymkeric substance that contains methyl methacrylate and 2-acrylamide-2-methyl propane sulfonic segment by the mode of atom transfer radical polymerization, this parents' polymkeric substance can self-assembly form micella in water, guide the polymerization of aniline using this micella as polymerizing template, the Nano particles of polyaniline obtaining is very even, substantially become monodispersity, and can regulate (Tracy Bucholz to the particle diameter of last Nano particles of polyaniline by the ratio that regulates methyl methacrylate and 2-acrylamide-2-methyl propane sulfonic segment, Yangming Sun and Yueh-Lin Loo, Near-monodispersed polyaniline particles through template synthesis and simultaneous doping withdiblock copolymers of PMA and PAAMPSA, J.Mater.Chem., 2008, 18, 5835-5842).But prepared by segmented copolymer loaded down with trivial details, need special catalyzer, required condition is harsher, and cost is high, is not suitable for large batch of production.And random parents' multipolymer is similar to segmented copolymer, in the aqueous solution, also can be self-assembled into micella, and its preparation is simple, simple radical polymerization can complete.Therefore this patent adopts radical polymerization to synthesize random parents' polymkeric substance, the Nano particles of polyaniline that utilizes its micella that self-assembly forms in water to prepare size evenly as polymerizing template and can water-dispersion, thus and give Nano particles of polyaniline photosensitivity by introduce photosensitivity group in this parents' polymkeric substance.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of photosensitive conductive polyaniline nanoparticles, this preparation method adopts photosensitivity parents polymer micelle as polymerizing template and stablizer, and simple efficiency is high.The Nano particles of polyaniline size obtaining evenly, the water dispersible having had, and can carry out photo-crosslinking, be a kind of eco-friendly photosensitivity electrical-conductive nanometer particle, the film forming properties also having had, can be for aspects such as photocuring electrically conducting coating, sensor and nanoparticle spray ink Printings.
The technical scheme that realizes the object of the invention is:
The first step, preparation has parents' polymkeric substance that can uv irradiation photo-crosslinking.
Second step adds deionized water by the parents' polymkeric substance obtaining in the first step under agitation condition, makes photosensitivity parents polymer micelle solution.
The 3rd step adds aniline monomer in above-mentioned photosensitive polymers micellar solution, then at low temperatures, adds the mixed solution of oxygenant and mineral acid, makes aniline generation polymerization.After completion of the reaction, obtain the solution containing photosensitivity Nano particles of polyaniline.
The 4th step, solution centrifugal, washing that the 3rd step is obtained, obtain photosensitivity Nano particles of polyaniline.
Major advantage of the present invention is:
The present invention is take photosensitivity parents polymer micelle as polymerizing template, prepare conductive polyaniline nanoparticles by chemical oxidative polymerization, by regulating ratio and the molecular weight of hydrophilic and oleophilic segment of parents polymkeric substance, can control the pattern of obtained Nano particles of polyaniline, size and performance.And the existence of parents' polymkeric substance can disperse Nano particles of polyaniline in water, its processing characteristics and environment friendly are improved, the film forming properties that the nanoparticle dispersion liquid obtaining has also had.In parents' polymer template, prepared Nano particles of polyaniline photocrosslinking reaction has also been given in the existence of photosensitivity monomer, is expected to further expand its application.
Accompanying drawing explanation
Institute's accompanying drawing is the transmission electron microscope picture of prepared photosensitivity Nano particles of polyaniline.
Embodiment
Below in conjunction with embodiment, the present invention is further explained in detail the present invention in order to explain better.
Embodiment 1
Weigh 2-acrylamide-2-methyl propane sulfonic 2.45g, ethyl coumarin 0.62g, initiator Diisopropyl azodicarboxylate 0.072g is in 25mL dioxane, inflated with nitrogen 30 minutes, reacts 24h, cool to room temperature at 65 ℃, boil off unnecessary solvent, in ethylene dichloride, precipitation obtains pure multipolymer.This multipolymer is dissolved in the aqueous solution, is cooled to 0 ℃, add the hydrochloric acid soln of aniline (0.5g), property adds the ammonium persulfate aqueous solution containing 1.3g again, stirs 8 hours.The blackish green polyaniline dispersion liquid obtaining is carried out to centrifugal (10000rpm) separating-purifying and obtain photosensitive conductive polyaniline nanoparticles.
Embodiment 2
Weigh vinylformic acid 1.72g, 2-styracin acyl-oxygen ethyl-(methyl) acrylate 0.85g, initiator Diisopropyl azodicarboxylate 0.065g is in 25mL dioxane, inflated with nitrogen 30 minutes, at 65 ℃, react 24h, cool to room temperature, boils off unnecessary solvent, and in ethylene dichloride, precipitation obtains pure multipolymer.This multipolymer is dissolved in the aqueous solution, is cooled to 0 ℃, add the hydrochloric acid soln of aniline (0.78g), property adds the ammonium persulfate aqueous solution containing 1.9g again, stirs 8 hours.The blackish green polyaniline dispersion liquid obtaining is carried out to centrifugal (8000rpm) separating-purifying and obtain photosensitive conductive polyaniline nanoparticles.
Claims (5)
1. a preparation method for photosensitive conductive polyaniline nanoparticles, is characterized in that preparation process and condition are as follows:
The first step, using photosensitivity monomer and hydrophilic monomer as comonomer, adopt radical polymerization get everything ready can uv irradiation photo-crosslinking parents' polymkeric substance;
Wherein, photosensitivity monomer is selected from one or more in following a few class photosensitive monomer:
7-(4-vinyl benzyloxy base)-4-methylcoumarin, 2-styracin acyl-oxygen ethyl-(methyl) acrylate, 2-methylol-(4-methylcoumarin) oxygen ethyl-methacrylic ester, 7-vinylformic acid coumarin ester, 7-acrylyl oxy-ethyl-4-methylcoumarin ether, glycidyl methacrylate graft (methyl) coumarin ether, (methyl) acryloyl-oxy oxyethyl group polycaprolactone-based laurate, (methyl) acrylyl oxy-ethyl caffeic acid ester;
The charging capacity of such monomer when free-radical polymerized accounts for 10%～80% of monomer molar total amount;
Hydrophilic monomer be selected from following one or more: (methyl) vinylformic acid, 2-acrylamide-2-methyl propane sulfonic, styrene sulfonic acid, (N-sec.-propyl) acrylamide, N-Methyl pyrrolidone;
Second step adds deionized water by the parents' polymkeric substance obtaining in the first step under agitation condition, makes photosensitivity parents polymer micelle solution;
The 3rd step adds aniline monomer in above-mentioned photosensitive polymers micellar solution, stirs 0.5～2 hour, at low temperatures, add the mixed solution of oxygenant and mineral acid, make aniline generation polymerization, reaction times is 2～72 hours, after completion of the reaction, obtains the solution containing photosensitivity Nano particles of polyaniline;
Wherein, photosensitivity parents' polymkeric substance is 0.1: 1～20: 1 with the ratio of the consumption of aniline monomer, and aniline monomer is 1: 1～4: 1 with the ratio of the consumption of oxygenant, and the amount ratio of oxygenant and mineral acid is 1: 1～1: 5;
The 4th step, solution centrifugal, washing that the 3rd step is obtained, obtain photosensitivity Nano particles of polyaniline.
2. the preparation method of photosensitivity Nano particles of polyaniline according to claim 1, is characterized in that photosensitivity parents' polymer average molecular weight that the first step obtains is between 5000～100000.
3. the preparation method of photosensitivity Nano particles of polyaniline according to claim 1, is characterized in that in the 3rd step, oxygenant is ammonium persulphate, Potassium Persulphate, and mineral acid is hydrochloric acid, sulfuric acid or nitric acid.
4. the preparation method of photosensitivity Nano particles of polyaniline according to claim 1, is characterized in that the particle diameter of prepared photosensitivity Nano particles of polyaniline is between 20～1000 nanometers.
5. the preparation method of photosensitivity Nano particles of polyaniline according to claim 1, is characterized in that prepared photosensitivity Nano particles of polyaniline can be scattered in the aqueous solution again, and the film forming properties that had of the nanoparticle dispersion liquid obtaining.
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| CN103613758B (en) * | 2013-12-03 | 2016-05-11 | 江南大学 | Self-assembly method is prepared molecular engram polyaniline nano compound |
| CN106083791B (en) * | 2016-06-08 | 2017-10-24 | 深圳市前海金卓生物技术有限公司 | A kind of coumarin derivative, its preparation method and by its obtained hydrogel |
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| US4851487A (en) * | 1988-02-22 | 1989-07-25 | Lockheed Corporation | Conductive polymer materials and method of producing same |
| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101302296A (en) * | 2008-06-03 | 2008-11-12 | 江南大学 | Preparation of amphiphilic copolymer self-assembled micelle wedding agent |
| CN101812182A (en) * | 2010-02-02 | 2010-08-25 | 江南大学 | Preparation method of photoelectric sensitive charged nanometer particles |
| CN101935373A (en) * | 2010-08-05 | 2011-01-05 | 江南大学 | Preparation method of multi-sensitivity photosensitive polyamphoteric electrolyte micelle |
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Patent Citations (5)
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| US4851487A (en) * | 1988-02-22 | 1989-07-25 | Lockheed Corporation | Conductive polymer materials and method of producing same |
| CN101225204A (en) * | 2007-12-25 | 2008-07-23 | 北京科技大学 | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres |
| CN101302296A (en) * | 2008-06-03 | 2008-11-12 | 江南大学 | Preparation of amphiphilic copolymer self-assembled micelle wedding agent |
| CN101812182A (en) * | 2010-02-02 | 2010-08-25 | 江南大学 | Preparation method of photoelectric sensitive charged nanometer particles |
| CN101935373A (en) * | 2010-08-05 | 2011-01-05 | 江南大学 | Preparation method of multi-sensitivity photosensitive polyamphoteric electrolyte micelle |
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| "Near-monodispersed polyaniline particles through template synthesis and simultaneous doping with diblock copolymers of PMA and PAAMPSA";Tracy Bucholz et al.;《Journal of Materials Chemistry》;20081104;第18卷;5835-5842 * |
| "光敏共聚物P(St/VM-co-MA)自组装胶体粒子及其性能";赵艳琼等;《物理化学学报》;20101104;第26卷(第12期);3230-3236 * |
| Tracy Bucholz et al.."Near-monodispersed polyaniline particles through template synthesis and simultaneous doping with diblock copolymers of PMA and PAAMPSA".《Journal of Materials Chemistry》.2008,第18卷5835-5842. |
| 赵艳琼等."光敏共聚物P(St/VM-co-MA)自组装胶体粒子及其性能".《物理化学学报》.2010,第26卷(第12期),3230-3236. |
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